US3898322A - Alumina having a binodal pore volume distribution - Google Patents

Alumina having a binodal pore volume distribution Download PDF

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US3898322A
US3898322A US31569672A US3898322A US 3898322 A US3898322 A US 3898322A US 31569672 A US31569672 A US 31569672A US 3898322 A US3898322 A US 3898322A
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alumina
pore volume
method
pores
aqueous alumina
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Bruce E Leach
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Vista Chemical Co
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Conoco Inc
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    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01FCOMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
    • C01F7/00Compounds of aluminium
    • C01F7/02Aluminium oxide; Aluminium hydroxide; Aluminates
    • C01F7/34Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts
    • C01F7/36Preparation of aluminium hydroxide by precipitation from solutions containing aluminium salts from organic aluminium salts
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/10Solid density
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/12Surface area
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/14Pore volume
    • CCHEMISTRY; METALLURGY
    • C01INORGANIC CHEMISTRY
    • C01PINDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00Physical properties of inorganic compounds
    • C01P2006/16Pore diameter

Abstract

Alpha alumina monohydrate having a cumulative pore volume from about 1.0 to about 3.0 cc/g wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A and a method for preparing such alumina.

Description

llited States Leach Aug. 5, 1975 [54] ALUMINA HAVING A BINODAL PORE 3,417,028 12/1968 Montgomery et al. 1. 423/628 x VOLUME DISTRIBUTION [75] Inventor: Bruce E. Leach, Ponca City, Okla.

[73] Assignee: Continental Oil Company, Ponca City, Okla.

[22] Filed: Dec. 15, 1972 [21] Appl. No: 315,696

[52] US. Cl. 423/628; 423/630; 423/625; 252/463 [51] Int. Cl. COlf 7/02 [58] Field of Search 423/625, 630, 628

[56] References Cited UNITED STATES PATENTS 3,264,063 8/1966 Carter 423/630 3,419,352 12/1968 Acciani 423/630 Primary Examiner-Herbert T. Carter Attorney, Agent, or F irmF. Lindsey Scott 5 7 ABSTRACT Alpha alumina monohydrate having a cumulative pore volume from about 1.0 to about 3.0 cc/g wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A and a method for preparing such alumina.

5 Claims, 3 Drawing Figures PATENTED 5W5 3,898,322

SHEET 1 PORE DIAMETER (A) 0 (6/00) BWO'IOA 380d PATENTEU AUG 5W5 OOI ( awn-loA 380d ALUMINA HAVING A BINODAL PORE VOLUME DISTRIBUTION FIELD OF THE INVENTION This invention relates to alumina. This invention further relates to alumina having a binodal pore volume distribution. This invention further relates to alumina having a binodal pore volume distribution and a method for preparing such alumina.

PRIOR ART Numerous processes, such as the water hydrolysis of aluminum alkoxide, the alum process, and sodium alu minate processes, are known for the production of alumina. Such alumina has a variety of uses, such as for catalysts, catalyst supports, and the like. In many of these applications, the usefulness of the alumina is directly related to the pore volume, surface area, and density. Generally, lighter alumina having low bulk density, high surface area and high porosity is more desirable. Most processes produce alumina having a loose bulk density greater than about 35 lb/ft, a pore volume of less than about 0.6 cc/g, and a surface arealower than about 275 m /g. Recently, it has been discovered that alumina slurry produced by the water hydrolysis of aluminum alkoxide; the alum process and sodium aluminate processes may be contacted with an effective amount of an organaic solvent having a lower surface tension than water to form a solvent-aqueous alumina mixture and dried to produce an alumina having a loose bulk density of about 7.5 to about 25 lb/ft, a surface area of about 275 to 400 m /g and a pore volume of from about 1 to about 2.75 cc/g. Such alumina is very desirable in catalytic applications and the like.

Even though the alumina having such properties is desirable as a catalyst, catalyst support, and the like, it has been observed that the pore volume is rather evenly distributed, and it has been postulated that for a number of liquid-phase reactions, a catalyst support having a large number of both small pores and large pores may be very desirable. Some applications for which such catalysts would be desirable are the demetalization of hydrocarbon feedstocks, hydrodesulfurization, and the like.

As a result, much time and effort has been directed to the development of an alumina having a large number of small pores and a large number of larger pores.

OBJECTS OF THE INVENTION It is the object of the present invention to provide an alumina having a high proportion of the cumulative pore volume in small pores and a high proportion of the cumulative pore volume in larger pores. It is a further objective of the present invention to provide a method for producing such alumina.

SUMMARY OF THE INVENTION It has been discovered that the objectives of the present invention are achieved in alpha alumina monohydrate having a cumulative pore volume (O10,000 A) from about 1.0 to about 3.0 cc/g, wherein from about to about 40 percent of the cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A. Such alumina is produced by a process comprising hydrolyzing solid aluminum alkoxides with water at a pH from about'4 to about 10 to produce aqueous alumina slurry and alcohol, contacting the aqueous alumina slurry with an effective amount of an organic solvent, having a lower surface tension than water, and drying to produce the desired alumina product.

DESCRIPTION OF THE DRAWING FIG. 1 shows the pore volume distribution of the alumina produced in Example 1.

FIG. 2 shows the pore volume distribution of the alumina produced in Example 2.

FIG. 3 shows the pore volume distribution of the alumina produced in Example 3.

DESCRIPTION OF PREFERRED EMBODIMENTS Alpha alumina monohydrate, having a cumulative pore volume (010,000 A) from about 1.0 to about 3.0 cc/g, wherein from about 20 to about 40 percent of the cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 20 to about 40 percent of the cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A is useful as catalyst, catalyst support, and the like. While such alumina is desirable and useful as a catalyst, catalyst support, and the like, preferred aluminas are those having a cumulative pore volume of about 1.5 to about 2.5 cc/g, wherein from about 20 to about 35 percent of the cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 25 to about 40 percent of the cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A. The more desirable aluminas are those having a cumulative pore volume from about 1.5 to about 2.5 cc/g, wherein from about 25 to about 35 percent of the cumulative pore volume consists of pores having a pore diameter from about 40 to about A and wherein from about 30 to about 40 percent of the cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A.

Such alumina is produced by a process comprising hydrolyzing solid aluminum alkoxides with water at a pH from about 4 to about 10 to produce an aqueous alumina slurry and alcohol, contacting the aqueous alumina slurry with an effective amount of an organic solvent, having a lower surface tension than water, and drying to produce alumina.

Aluminum alkoxides generally are suitable for use in the process of present invention; however, preferred aluminum alkoxides are those produced by the Ziegler process wherein the alkoxide groups, each of which contains from about 1 to about 30 carbon atoms.

In the practice of the present invention, it has been observed that most desirable results are achieved when the pH is from about 4 to about 6. The pH in the hydrolysis reaction may, of course, be adjusted by means well known to those skilled in the art, such as the addition of alkaline or acidic material such as ammonium hydroxide, inorganic and organic acids, and the like.

It is usually necessary to separate the aqueous alumina slurry and the alcohol by means well known to those skilled in the arts, such as filtration, centrifugation, and the like, and in addition, other steps may be employed to result in more complete separation of the aqueous alumina slurry and the produced alcohols. In some instances where the alcohol produced has a low molecular weight, it may not be necessary to separate theaqueous alumina slurry and the alcohol.

The aqueous alumina slurry is contacted with aneffective amount of an organic solvent and dried to pro-- duce the desired alumina product. A process for contacting aqueous alumina slurries with organic solvents to produce alumina having higher surface areas, lower loose bulk densities, and higher pore volumes is disclosed in U.S. Ser. No. 246,028 entitled High Porosity, High Surface Area, Low Bulk Density Alumina,

filed Apr. 20, 1972, by W. C; Ziegenhain. Suitable organic solvents are selected from the group consisting of acetone, methanol, ethanol, propanol, isopropanol, bu-

tano l, isobutanol, andtertiary butanol, and desirably,

the organic solvent is presentin an amount sufficient to form an azeotropic mixturc with thewater present so that upon drying, the water is removed azeotropically.

It has further been found that most desirable results are achieved when the aqueous alumina slurry is aged after hydrolysis for at least two hours. It is preferred I that the aqueous alumina slurrybc aged for at least 24 hours, although desirable results have been obtained wherein the aqueous alumina slurry was'aged from about 2 to about 60 hours.

The alumina product of the present invention may be extruded to produce extrudates having a cumulative pore volume from about 1.5 to about 3.0 cc/g wherein from'about to about 35 percent of the cumulative pore volume consists of pores from about 40 to about .80 A in diameter and wherein from about 25 to about percent of the cumulative pore volume consists of pores from about 250 to about 800 A in diameter. Such extrudates may be produced by methodswell known in the, art, such as the methods disclosed in U.S.,Ser. No;

268,246 entitled Low Density, High Porosity Alumina Extrudates and the Methods for Producing Said Extrudates filed July 3, 1972, by Leach et al. Such ex-.

is present as pores having a relatively large pore diameter.

It is pointed out'thatthe foregoing description of pre- Loose bulk densityv Surface area Thermogravimetric analysis Cumulative pore volume Pore Volume Distribution Pore Diameter Cumulative Pore Volume cc/g O 35 0.0l O 40 0.07 0 V 0.36 0 65 0.50 0 80 0.56 0 100 (167 0 120 v 0.73 0 150 0.84 0 200 L00 0 250 L16 0 350 1.42 0 500 v 1.72 0 800 1.82 0 1,000 I 1.89 O 2,000 L93 0 I 5,000 2.01

EXAMPLE 2 'Aluminum alkoxides produced by the Ziegler process were hydrolyzed at 200F in the presence of 0.25 weight percent ammonia. The alumina slurry was separated from the alcohols and contacted with an azeotropic-amount of normal butanol and dried. The resultferred embodiments is illustrative in nature and should not be considered as limiting'ln fact it is expected that upon a reviewof theforegoing description of preferred embodiments and the appended examples and claims,

many variations and modifications within the scope. of the presenttinvention may appear obvious and desirable to those skilled in the art. I

EXAMPLE 1 tially complete in a few hours, but the alumina was allowed to age at room temperature for 60 hours. The

aluminawas filtered and washed twice with 1 liter portions of anhydrous isopropanol before drying. The alumina had the following properties:

ing alumina had a'porevolume distribution as shown below:

Pore Volume Distribution Pore Diameter, Cumulative Pore Volume A 1 cc/g 0 40 I 0.01 0 50 0.05 0- v r 0.28 0 so 3 0.48 0 0.62 0 I I 0.70 0 0.80 0 200 0.91 0 250 1.01 0 350v 1.10 0- 500' 1.32 0 800 V 1.46 0 1,000 1.57 0 2,000 1.71 0 5,000 1.93 0- 10,000 V 2.17

The pore volume distribution is shown in tabular form in FIG. 2, and it will be observed that the unusual binodal pore volume distribution shown in Example 1 is not present.

EXAMPLE 3 Example 1 was repeated except that the hydrolysis aging time was shortened to 24 hours. The alumina product had the following properties:

Loose bulk density 12.5 lb/ft" Surface area 363 m /g Cumulative pore volume 2.03 cc/g Pore Volume Distribution Cumulative Pore Volume Pore Diameter A cc/g EXAMPLE 4 The alumina produce from Example 1 was pelleted and compared with an extrudate of the alumina product of Example 2.

Pore Volume Distribution Cumulative Pore Volume Pore Diameter cc/g Pellet 1' cc/g Extrudate It is recognized that many of the steps included in the method of the present invention are well known to those skilled in the art, and no novelty is claimed in such steps. The novelty in the present method lies in the combination of the steps in the particular manner shown to produce an unusual and unexpected alumina product having a binodal pore volume distribution.

Having thus described the invention, 1 claim:

1. A method for producing alpha alumina monohydrate having a cumulative pore volume 010,000A from about 1.0 to about 3.0 cc/g wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 40 to about 100 A and wherein from about 20 to about 40 percent of said cumulative pore volume consists of pores having a pore diameter from about 250 to about 800 A, said method consisting essentially of sequentially:

a. hydrolyzing solid aluminum alkoxides with water having a pH from about 4 to about 10 to produce an aqueous alumina slurry and alcohol,

b. mixing said aqueous alumina slurry with an organic solvent selected from the group consisting of acetone, methanol, ethanol, propanol, isopropanol, butanol, isobutanol and tertiary butanol in an amount sufficient to form an azeotropic mixture with the water present in said aqueous alumina slurry to form a solvent-aqueous alumina mixture and c. drying said mixture to produce said alpha alumina monohydrate.

'2. The method of claim 1 wherein said pH is from about 4 to about 6. I 3. The method of claim 1 wherein aqueous alumina slurry is aged after hydrolysis for at least 2 hours.

,4. The method of claim 3 wherein said aqueous alumina slurry is aged from about 2 to about 60 hours.

5. The method of claim 1 wherein said aqueous alumina slurry is aged after hydrolysis for at least 24 hours. l l

UNITED STATES PATENT OFFICE QERHFICATE OF CORRECTION PATENT NO. 3 ,898,322

DATED 1 August 5, 1975 INVENTOR(S) :Bruce Leach It is certified that error appears in the sbeveAdentifie-d patent and that said Letters Patent Q are hereby corrected as shown below:

Column 2, line 34, "The more" should be changed to read The most a Column 2, line 53, between the words "alkoxide" and "group" the words portion of the alumina alkoxide consists of alkoxide should be inserted.

Signed and Sealed this J twenty-third 1y of March 1 9 76 [SEAL] Arrest:

Q RUTH C. MASON C. MARSHALL DANN Arresting Officer (ommixsr'uner ufPatenIs and Trademarks

Claims (5)

1. A METHOD FOR PRODUCING ALPHA ALUMINA MONOHYDRATE HAVING A CUMULATIVE PORE VOLUE 0-10,000A FROM ABOUT 1.0 TO ABOUT 3.0 CC/G WHEREIN FROM ABOUT 20 TO ABOUT 40 PERCENT OF SAID CUMULATIVE PORE VOLUME CONSISTS OF PORES HAVING A PORE DIAMETER FROM ABOUT 40 TO ABOUT 100 A AND WHEREIN FROM ABOUT 20 TO ABOUT 40 PERCENT OF SAID CUMULATIVE PORE VOLUME CONSISTS OF PORES HAVING A PORE DIAMETER FROM ABOUT 250 TO ABOUT 800 A, SAID METHOD CONSISTING ESSENTIALLY OF SEQUENTIALLY: A. HYDROLYZING SOLID ALUMINUM ALKOXIDES WITH WATER HAVING A PH FROM ABOUT 4 TO ABOUT 10 TO PRODUCE AN AQUEOUS ALUMINA SLURRY AND ALCOHOL, B. MIXING SAID AQUEOUS ALUMINA SLURRY WITH AN ORGANIC SOLVENT SELECTED FROM THE GROUP CONSISTING OF ACETONE, METHANOL, ETHANOL, PROPANOL, ISOPROPANOL, BUTANOL, ISOBUTANOL AND TERITARY BUTANOL IN AN AMOUNT SUFFICIENT TO FORM AN AZEOTROPIC MIXTURE WITH THE WATER PRESENT IN SAID AQUEOUS ALUMINA SLURRY TO FORM A SOLVENT-AQUEOUS ALUMINA MIXTURE AND C. DRYING SAID MIXTURE TO PRODUCE SAID ALPHA ALUMINA MONOHYDRATE.
2. The method of claim 1 wherein said pH is from about 4 to about 6.
3. The method of claim 1 wherein aqueous alumina slurry is aged after hydrolysis for at least 2 hours.
4. The method of claim 3 wherein said aqueous alumina slurry is aged from about 2 to about 60 hours.
5. The method of claim 1 wherein said aqueous alumina slurry is aged after hydrolysis for at least 24 hours.
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Cited By (22)

* Cited by examiner, † Cited by third party
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US3959179A (en) * 1974-09-23 1976-05-25 Mobil Oil Corporation Desulfurization catalysts
US4045372A (en) * 1975-08-20 1977-08-30 W. R. Grace & Co. Control of physical properties of alumina extrudates
US4169883A (en) * 1978-07-25 1979-10-02 Exxon Research & Engineering Co. Process for preparing ultra-stable, high surface area alpha-alumina
US4175118A (en) * 1975-12-17 1979-11-20 Condea Chemie Gmbh Method for manufacturing a high porous alumina having a large surface area and a low bulk density
US4248852A (en) * 1978-08-15 1981-02-03 Chiyoda Chemical Engineering & Construction Co., Ltd. Process for the production of alumina suitable for use as a catalyst carrier
US4275052A (en) * 1980-05-02 1981-06-23 Uop Inc. Process for preparing high surface area aluminas
US4301037A (en) * 1980-04-01 1981-11-17 W. R. Grace & Co. Extruded alumina catalyst support having controlled distribution of pore sizes
US4532121A (en) * 1981-06-02 1985-07-30 Produits Chimiques Ugine Kuhlmann Process for the preparation of finely divided aluminas or alumina-magnesia spinels having homogeneous pore structure
US4704378A (en) * 1987-02-19 1987-11-03 Aluminum Company Of America Fluidized bed granulation of rehydratable alumina
US4791090A (en) * 1986-05-02 1988-12-13 W. R. Grace & Co.-Conn. Hydroprocessing catalyst and support having bidisperse pore structure
US4797271A (en) * 1987-02-19 1989-01-10 Aluminum Company Of America Producing alumina granules in a fluidized bed
DE3823895C1 (en) * 1988-07-14 1989-12-21 Condea Chemie Gmbh, 2212 Brunsbuettel, De
US5032379A (en) * 1984-11-13 1991-07-16 Aluminum Company Of America Alumina suitable for catalytic applications
WO1992002456A1 (en) * 1985-03-18 1992-02-20 Aluminum Company Of America Alumina suitable for catalytic applications
US5231066A (en) * 1991-09-11 1993-07-27 Quantum Chemical Corporation Bimodal silica gel, its preparation and use as a catalyst support
US5354548A (en) * 1985-05-01 1994-10-11 Unilever Patent Holdings B.V. Porous three-dimensional inorganic oxide structure with myriad cavities interconnected by holes
US6110862A (en) * 1998-05-07 2000-08-29 Engelhard Corporation Catalytic material having improved conversion performance
US6303531B1 (en) 1999-12-21 2001-10-16 W. R. Grace & Co.-Conn. Hydrothermally stable high pore volume aluminum oxide/swellable clay composites and methods of their preparation and use
US6403526B1 (en) 1999-12-21 2002-06-11 W. R. Grace & Co.-Conn. Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use
US6451200B1 (en) 2000-01-13 2002-09-17 W. R. Grace & Co.-Conn. Hydrothermally stable high pore volume aluminum oxide/swellable clay composites and methods of their preparation and use
US6773690B1 (en) 1998-08-14 2004-08-10 Sasol Germany Gmb Boehmitic aluminas, and high-temperature stabile and highly porous aluminum oxides in a pure phase which are obtained therefrom
US9108188B2 (en) 2012-03-07 2015-08-18 Chevoron Phillip Chemical Company, LP Selective hydrogenation catalyst and methods of making and using same

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DE3503668A1 (en) * 1985-02-04 1986-08-07 Vaw Ver Aluminium Werke Ag A method for producing ceramic formkoerper
US5863515A (en) * 1996-02-20 1999-01-26 California Institute Of Technology Mesoporous alumina and process for its preparation
JP4818163B2 (en) * 2007-03-01 2011-11-16 日揮触媒化成株式会社 Alumina support and hydrodemetallization catalysts and methods for their preparation using the same

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US3417028A (en) * 1961-07-03 1968-12-17 Montgomery Douglas Sargent Process for the preparation of an inorganic gel having a predetermined pore structure
US3419352A (en) * 1964-12-02 1968-12-31 Continental Oil Co Process for producing alpha alumina monohydrate

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US3417028A (en) * 1961-07-03 1968-12-17 Montgomery Douglas Sargent Process for the preparation of an inorganic gel having a predetermined pore structure
US3264063A (en) * 1964-11-05 1966-08-02 Continental Oil Co Preparation of eta alumina by water hydrolysis
US3419352A (en) * 1964-12-02 1968-12-31 Continental Oil Co Process for producing alpha alumina monohydrate

Cited By (31)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3959179A (en) * 1974-09-23 1976-05-25 Mobil Oil Corporation Desulfurization catalysts
US4045372A (en) * 1975-08-20 1977-08-30 W. R. Grace & Co. Control of physical properties of alumina extrudates
US4175118A (en) * 1975-12-17 1979-11-20 Condea Chemie Gmbh Method for manufacturing a high porous alumina having a large surface area and a low bulk density
US4169883A (en) * 1978-07-25 1979-10-02 Exxon Research & Engineering Co. Process for preparing ultra-stable, high surface area alpha-alumina
US4248852A (en) * 1978-08-15 1981-02-03 Chiyoda Chemical Engineering & Construction Co., Ltd. Process for the production of alumina suitable for use as a catalyst carrier
US4301037A (en) * 1980-04-01 1981-11-17 W. R. Grace & Co. Extruded alumina catalyst support having controlled distribution of pore sizes
DE3113326A1 (en) * 1980-04-01 1982-04-08 Grace W R & Co Thermally stable alumina extrudate controlled porengroessenverteilung, its manufacture and its use
US4275052A (en) * 1980-05-02 1981-06-23 Uop Inc. Process for preparing high surface area aluminas
US4532121A (en) * 1981-06-02 1985-07-30 Produits Chimiques Ugine Kuhlmann Process for the preparation of finely divided aluminas or alumina-magnesia spinels having homogeneous pore structure
US5032379A (en) * 1984-11-13 1991-07-16 Aluminum Company Of America Alumina suitable for catalytic applications
WO1992002456A1 (en) * 1985-03-18 1992-02-20 Aluminum Company Of America Alumina suitable for catalytic applications
US5354548A (en) * 1985-05-01 1994-10-11 Unilever Patent Holdings B.V. Porous three-dimensional inorganic oxide structure with myriad cavities interconnected by holes
US4791090A (en) * 1986-05-02 1988-12-13 W. R. Grace & Co.-Conn. Hydroprocessing catalyst and support having bidisperse pore structure
US4797271A (en) * 1987-02-19 1989-01-10 Aluminum Company Of America Producing alumina granules in a fluidized bed
US4704378A (en) * 1987-02-19 1987-11-03 Aluminum Company Of America Fluidized bed granulation of rehydratable alumina
US5055019A (en) * 1988-07-14 1991-10-08 Condea Chemie Gmbh Process for the production of boehmitic aluminas
DE3823895C1 (en) * 1988-07-14 1989-12-21 Condea Chemie Gmbh, 2212 Brunsbuettel, De
US5231066A (en) * 1991-09-11 1993-07-27 Quantum Chemical Corporation Bimodal silica gel, its preparation and use as a catalyst support
US5321105A (en) * 1991-09-11 1994-06-14 Quantum Chemical Corporation Polymerization process using a bimodal silica gel as a catalyst support
US6110862A (en) * 1998-05-07 2000-08-29 Engelhard Corporation Catalytic material having improved conversion performance
US20080305333A1 (en) * 1998-08-14 2008-12-11 Klaus Noweck Boehmitic Aluminas and High-Temperature Stable, High-Porosity, Pure-Phase Aluminium Oxides Obtained Therefrom
EP2258659A2 (en) 1998-08-14 2010-12-08 SASOL Germany GmbH Boehmitic aluminas, and high-temperature stabile and highly porous aluminum oxides in a pure phase which are obtained therefrom
US8414854B2 (en) 1998-08-14 2013-04-09 Sasol Germany Gmbh Boehmitic aluminas and high-temperature stable, high-porosity, pure-phase aluminium oxides obtained therefrom
US6773690B1 (en) 1998-08-14 2004-08-10 Sasol Germany Gmb Boehmitic aluminas, and high-temperature stabile and highly porous aluminum oxides in a pure phase which are obtained therefrom
US20050019249A1 (en) * 1998-08-14 2005-01-27 Klaus Noweck Boehmitic aluminas and high-temperature stable, high-porosity, pure-phase aluminium oxides obtained therefrom
US6403526B1 (en) 1999-12-21 2002-06-11 W. R. Grace & Co.-Conn. Alumina trihydrate derived high pore volume, high surface area aluminum oxide composites and methods of their preparation and use
US6303531B1 (en) 1999-12-21 2001-10-16 W. R. Grace & Co.-Conn. Hydrothermally stable high pore volume aluminum oxide/swellable clay composites and methods of their preparation and use
US6451200B1 (en) 2000-01-13 2002-09-17 W. R. Grace & Co.-Conn. Hydrothermally stable high pore volume aluminum oxide/swellable clay composites and methods of their preparation and use
US9108188B2 (en) 2012-03-07 2015-08-18 Chevoron Phillip Chemical Company, LP Selective hydrogenation catalyst and methods of making and using same
US9144787B2 (en) 2012-03-07 2015-09-29 Chevron Phillips Chemical Company Lp Selective hydrogenation catalyst and methods of making and using same
US9636659B2 (en) 2012-03-07 2017-05-02 Chevron Phillips Chemical Company Lp Selective hydrogenation catalyst and methods of making and using same

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